Carbamates and thiolcarbamates

ABSTRACT

Certain novel carbamates and thiolcarbamates are broad spectrum herbicides, which can be applied to the locus of undesired vegetation either preemergence or postemergence. Typical representatives of this class of compounds are methyl N-(Ncyclohexylcarbamoyl-N&#39;&#39;,N&#39;&#39;-dimethylamidino)-N-methylcarbamate and methyl N-(1-(3-cyclohexyl-1-methylureido)-1dimethylaminomethylene)carbamate.

United States Patent 1 Fuchs May 6, 1975 CARBAMATES AND THIOLCARBAMATES[75] Inventor: Julius Jakob Fuchs, Wilmington,

Del.

[73] Assignee: E. 1. du Pont de Nemours Company,

Wilmington, Del.

[22] Filed: May 2, 1973 [21] Appl. N0.: 356,422

Related US. Application Data [63] Continuation-impart of Serv No.312,904, Dec. 7,

1972, Pat. No. 3,823,179.

[52] US. Cl 260/468 E; 260/455 A; 260/465.4; 260/470; 260/471 C; 260/481C; 260/482 C; 260/564 R, 71/99; 71/100; 71/106; 71/111;

[51] Int. Cl. C07c 129/12 [58] Field of Search 260/468 E [56] ReferencesCited UNITED STATES PATENTS 3,388,113 6/1968 Guttmann et a1. 260/482 C3,564,041 2/1971 Farrisey et al. 260/471 OTHER PUBLICATIONS Junod,Heluectica Chimica Acta., v01. 35, (1952), PP. 1,005-1 ,01 5

Primary ExaminerLorraine A. Weinberger Assistant Examiner-MichaelShippen [57] ABSTRACT 4 Claims, No Drawings CARBAMATES ANDTHIOLCARBAMATES CROSS-REFERENCE TO RELATED APPLICATION This is acontinuation-in-part of my copending appliwherein Q is hydrogen,fluorine, chlorine, bromine, a C C. alkyl, a C -C alkoxy or alkylthiogroup, nitro or trifluoromethyl group;

cation Ser. NO. DEC. 7, 110W Y is hydrogen chlg ine or methyl; and3,823,179- Z is hydrogen or chlorine;

SUMMARY OF THE INVENTION R2 f 3 alkyl;

R; IS hydrogen, methyl, or ethyl; According to the present invention, ithas now been R i a (I -C lk l, 3 (f -(J alkenyl, a C -C alkynyl,discovered that certain novel carbamates and thiolcaror h bamates areeffective and readily available herbicides. R5 is ()R6 or SR6 Thecompounds of this invention can be represented by wherein R6 is a CFCBalky] substituted with 3 h1 the isomeric Formulas l and (2), whichdiffer only in fine atoms or methoxyl; and the position of thesubstituent R with a concomitant X is Oxygen or Sum". shift of thedouble bond.

R R The compounds of this invention can be applied to 3 u the locus ofweeds either preemergence or postemer- X N 0 gence and provide excellentprotection against a broad R E E (l spectrum of weeds.

2 R3 \N 4 3E 9 DETAILED DESQRIPTION OF THE INVENTION g fi (2) Especiallyhighly active and, therefore, preferred R compounds of the presentinvention are those com- 2 pounds represented by the above Formulas (I)and wherein 2), wherein 1 is Selefled from a C2-C8 alkyl Substitutedwith R is alkyl of 3 through 6 carbon atoms, cycloalkyl of methoxy,ethoxy, methylthio, or ethylthio group; a 5 th h 8 bon atoms, orcycloalkyl of 5 3- 6 ny a 3- 6 y y a 4- 3 cycloalkyl through 8 carbonatoms substituted with one substituted with 0-1 C -C alkyl, 0-2 methylmethyl group; groups, 0-2 chlorine or bromine atoms, or 0-1 R R and R,are methyl; and methoxy or ethoxy group; a C -C cycloalkenyl; a R i ORC,,-C cycloalkylmethyl or cycloalkenylmethyl; a Particularly preferredwithin this class are those comr m blcycloalkyl or blcycloalkenyl; a 8-1: pounds of Formulas (I) and (2) where bicycloalkylmethyl orbicycloalkenylmethyl; trime- R is cyclopentyl, methylcyclopentyl,cyclohexyl 0r thylcyclohexyl; tetramethylcyclohexyl; and th l l h l;

Q X is oxgen; and

z R is methoxyl.

The following reaction sequence I, which illustrates the preparation ofmethyl N( N-cyclohexylcarbamoyl- N,N-dimethylamidino)-N-methylcarbamate, is suitable for the preparation ofmost of the compounds of Seguence I Formula (I) contemplated by thisdisclosure:

0 NaOH ll N-CN 2 611 0 C Cl CHBG C I? CN O O H CH O-C-N-CN SD (:5O-C-N-CN CH CH 3 3 O O N n (CH 'HCI n I B) CH3O-C-NCN CH 0CN-C-Nl'l 2)NBOH CH3 3 on CH CH CH 0 0 N O +H anawv -c-nc) CH O-C 1:: 0 NH N Othercompounds of Formula l contemplated by this disclosure can besynthesized by a reaction of appropriate alkylcyanamides with where Rhas the above-defined meaning.

This reaction is shown below as the first step of Sequence ll.

The following reaction sequence Ill, which illustrates the preparationof methyl N-[ l-cyclohexyl-lmethylureido)-l-dimethylaminomethylene]carbamate is suitable for the preparation of thecompounds of the isomeric Formula (2).

Seguence III CH CH H3 CH3 o CH CH.

+CH NH 3 CH SH cg /CH 3 f f? NCO n) HN-C=N-C-OCH3 N CH CH o\N/O u un-c-ti-cm-c-ocn These preparations are described in the following Examples,wherein all the proportions, parts, and percentages are by weight.

EXAMPLE 1 A. Synthesis of N-Methoxycarbonyl-N-Methylcyanamide To asolution of 504 parts of a 50% aqueous cyanamide solution in 825 partsof water at 25C. are added during a period of 90 minutes and at a pH of6.9-7.1 simultaneously 572 parts of methyl chloroformate and 945 partsof a 50% aqueous sodium hydroxide solution. As the addition of thereactants progresses, the temperature of the reaction is allowed to riseto 535 5C. and is maintained within that range by cooling. When theaddition is complete, the reaction mass is cooled to 25C., whereuponcrystallization of the sodium salt of methoxycarbonylcyanamide occurs.Dimethyl sulfate (775 parts) is then added, and agitation of thereaction mass is continued while maintaining the pH at 7-7.l by adropwise addition of about 25 parts of a 50 aqueous sodium hydroxidesolution. After 6.5 hours, the resulting two-phase solution isrepeatedly extracted with methylene chloride and the extract is dried.One half of the methylene chloride extract is then evaporated undervacuum, and the residue is distilled at 50C./0.5 mm. There is obtained237.6 parts of N- methoxycarbonyl-N-methylcyanamide (69.5% yield).

B. Synthesis of N-Methoxycarbonyl-N,N,N'-Trimethylguanidine A solutionof 339 parts of dimethylamine hydrochloride in 500 parts of water isheated to 50C., and the remaining one half of the above methylenechloride extract is added to it gradually, while at the same timeremoving the methylene chloride by distillation. The resulting two-phasemixture is then heated for approxi mately 20 hours at C., after whichtime the starting N-methoxycarbonyl-N-methylcyanamide has nearlycompletely disappeared. The solution is then cooled to 0C., and 336parts of a 50% aqueous sodium hydroxide is added. Repeated extraction ofthe reaction solution with methylene chloride and evaporation of themethylene chloride under vacuum gives 228.6 parts of crudeN-methoxycarbonyl-N,N',N-trimethylguanidine of 84.4% purity, from whichthe pure product is isolated by distillation at 72C./0.5 mm.

C. Synthesis of Methyl N-(N-cyclohexylcarbamoyl-N',N'-dimethylamidino)Nmethylcarbamate To 14.8 parts of the above crude N-methoxycarbonyl-N,N',N'-trimethylguanidine in 50 parts of methylenechloride is added I 1.0 parts of cyclohexyl isocyanate. The solutiontemperature reaches the boiling point, and when the temperature hasfallen to 25C., the solvent is evaporated under vacuum to give an oil,which crystallizes when triturated with either. Recrystallization from amixture of carbon tetra chloride and petroleum ether gives pure methylN-( N- The lower methylene chloride layer is removed, the pH adjusted to11.0 with 50% caustic, and aqueous phase extracted twice with 150 mls ofmethylene chloride. The combined extracts are evaporated to constantweight on a rotary evaporator to give 78.5 parts of crude methyl N-( 1-dimethylamino- 1 -methlthiomethylene)carbamate as an oil which ispurified by vacuum fractionation to give 59.8 parts of product, b.p.103C at 0.4 mm Hg.

C. Synthesis of Methyl N-( 1Dimethy1amin0-1-methylaminomethylene)carbamate The above distillate isadded to a solution of 28.6 parts of monomethylamine in 423 parts oftoluene and stirred in a closed system for 24 hours. The reaction massis then evaporated to constant weight on a rotary evaporator to give 55parts of an oil which solidifies on standing overnight, m.p. 8085C.Recrystallization from toluene-heptane gives 41.0 parts of methyl N-( 1-dimethylaminol -methylamino-methy1ene) carbamate as a pure whitecrystalline material, m.p. 87-89C.

D. Synthesis of Methyl N-[ l-( 3-Cyc1ohexyl-1-methylureido)- ldimethylaminomethylene]carbamate The above product is dissolved in asolution of 32.2 parts of cyclohexyl isocyanate in 510 parts of 1,2-dichloroethane and heated under reflux for 2 hours. The reaction mass iscooled to room temperature, and 586 parts of water is added. The pH ofthe resulting aqueous phase is adjusted to approximately 2 with conc.hydrochloric acid. The aqueous phase is separated, 1,020 parts of 1,2-dichloroethane added to it, and enough 50% caustic is added to adjustthe pH of the aqueous phase to to 11. The mixture is shaken and the1,2-dichloroethane layer evaporated to constant weight on a rotaryevaporator to give 43.0 gms of oil, which crystallizes on standing togive an impure solid, m.p. 60-75. Recrystallization from tolueneheptanegives 16.3 parts of methyl N-I 1-(3-cyc1ohexyl-1-methylureido)-1-dimethy1aminornethylene]carbamate as pure whitecrystals, m.p. 8182C.

Using the appropriate starting materials, the following compounds can beprepared in a similar manner. methyl N-[ 1-(3-n-pentyl-l-methylureid0)-1dimethylaminomethylene]carbamate methyl N-[ 1-(3-cyc1ohexylmethyll-methylureido)- 1 dimethylaminomethylene]carbamatemethyl N-[ l-(3-n-propy1-1-methylureido)-1-dimethylaminomethylene]carbamate methy N-[ 1-( 3-n-butyl- 1-methylureido I dimethylaminomethylene]carbamate methyl N-[ 1-(3-n-hexyll -methylureido 1 dimethylaminomethylene]carbamate methylN-[1-(3-n-octyl-l-methylureido)-1- dimethylaminomethylene]carbamatemethyl N- (l-[3-( l ,3-dimethylbutyl)-1-methylureido]-l-dimethylaminomethylene}carbamate methyl N-{1-[3-(1-ethylpropy1)-1-methylureido]-ldimethylaminomethylene}carbamate methylN- {1-[ 3-( 1-isopropyl-2-methy1propyl l methylureido 11dimethylaminomethylene}carbamate methyl N- {1-[3-( l,2,2-trimethy1propyl l methylureido1- l-dimethy1aminomethylene)carbamate methyl N-[ 1-( 3-neopentyll-methylureido)- l dimethylaminomethylene]carbamate methyl N- l 3-(1methylbutyl)- l -methylureido}- l dimethylaminomethylene lcarbamatemethylN-{1-[3-(3-trifluoromethylpheny1)-lmethylureido}1-dimethylaminomethylene]carbamatemethyl N-[ l-( 3-ethyl -1-isopropylureido)-l diethylaminomethylenel-carbamate methyl N-[ 1-( 3-butyl- 1 -propylureido)- l -methyl-1propylaminomethylene ]carbamate methyl N-[1-(3-octyl-1-methy1ureido)-1-allylaminomethylene -carbamate methyl N-{1-[3-(2-norbornyl)-1-methylureido]-1- dimethylaminomethylene carbamatemethyl N-[ 1-(3-phenyl-1methylureido)- 1dimethylaminomethylene]carbamate methyl N-{l- [3-(p-chlorophenyl l-methy1ureido]- 1 -dimethylaminomethylene carbamate methyl N- {.1-[3-(3,4-dichlorophenyl l methy1ureido]- 1dimethylaminomethylene}carbamateethyl N-[ 1-( 3-cyclohexy1- l -methylureido)- l dimethylaminomethylene]carbamate ethyl N-{ 1-( 3-cyclooctyll -methylureido)- ldimethylaminomethylene carbamate ethylN-[1-(3-phenyl-l-methylureido)-ldimethylaminomethylene carbamate ethylN- {1-[3-(m-tolyl)-Lmethylureidoll dimethylaminomethylene}-carbamateoctyl N-[ l -(3cyclohexyl1-methylureido)- 1 dimethylaminomethylene]carbamate methyl N 1-[ 3-(2-ethoxybutyl)- 1 -methy1ureido 1dimethylaminomethylene }carbamate methyl N- {l[3-(2-methylthiobuty1)-l-methylureido]- 1-dimethylaminomethylene}carbamate ethyl N-ll-[3-(2-ethylthiopropyl)-l-methylureido]ldimethylaminomethylene}carbamate hexyl N-[ 1-( 3-cyclohexyl- 1-methylureido) l dimethylaminomethylene ]carbamate hexylN-[1-(3-cyclopenty1-1-methylureido)-ldimethylaminomethylene]carbamatehexyl N-[ 1-( 3-phenyl- 1 -methylureido)1 dimethylaminomethylene]carbamate isopropyl N-[1-(3-cyc1ohexyl-1-methylureido)-ldimethylaminomethylene ]carbamateisopropyl N-[ 1 3-norbornyll -methylureido)- l dimethylaminomethylene]carbamate isopropyl N- {1-[3-(o-flourophenyl)-1-methylureido]-1-dimethylaminomethy1ene} carbamate isopropylN-{l-[3-(2-propenyl)-1-methylureido1-ldimethylaminomethylene} carbamatemethyl N- {1-[3-(3-methoxypropy1)-1-methylureido]- l-dimethylaminomethylene }carbamate methyl N- l l -[3-(2-chlorocyclohexyl)- l methylureido]- l-dimethylaminomethylene}carbamate methyl N- {l-[3-(2,3-dichlorocyclohexyl)-1methylureido]-1-dimethylaminomethylene}carbamate methyl N{l-[3-(2-bromocycl0hexyl)- l -methylureido] bromocyclohexyl- 1-methylureido] 1 -dimethylaminomethylene}carbamate methyl l-[3-(2-methylcyclohexyll-1-methy1ureido]-1- dimethylaminomethylene}carbamate methyl N-{ l 3-( 2,6-dimethylcyclohexyl lmethylureido1-1dimethylaminomethylene}carbamate methyl N- {l-[3-(2-butylcyclopentyl l -methylureido]- l-dimethylaminomethylenecarbamate methyl N-{l-{3-(2-norbornyl)-l-methylureido1-l-diethylaminomethylene }carbamatemethyl N- l-[ 3-cyclohexen-2-yl l -methylureido} ldimethylaminomethylene}carbamate methyl N- l-[ 3-(cyclopenten-2-yl)-l -methylureido]-1-dimethylaminomethylene}carbamate ethyl N{ l-(3-norbornyl-l-methylureido)-ldimethylaminomethyleneIcarbamate isopropylN-[ l-(3-norbornyll -methylureido l dimethylaminomethylene]carbamatemethyl N- {l 3-(4-isopropylcyclohexyl)- l methylureido]- l-dimethylaminomethylene}carbamate ethyl N- l 3-(p-tolyl l -methylureido]1 -dimethylaminomethylene )carbamate ethyl N- (l 3-(m-nitrophenyl)-l-methylureido]- l dimethylaminomethylene} carbamate ethyl N- l-[ 3-(3-chloro-4-isopropylphenyl l methylureido} l-dimethylaminomethylene)carbamate ethyl N- l 3-( 3-chloro4-nitrophenyl lmethylureidol- 1 dimethylaminomethylene} carbamate ethyl N- l-[3-(p-propylphenyl l -methylureido l dimethylaminomethylene }carbamatemethyl N-{ l-( 3-cyclohexyll -methylureido ldimethylaminomethylene]thiolcarbamate methyl N-[ l-( 3-cycloheptyll-methylureido) ldimethylaminomethylenelthiolcarbamate methyl N-[ l-(3-cyclopentyll -methylureido)- l dimethylaminomethylenelthiolcarbamatemethyl N- {l-[ 3-(2-methylcyclohexyl)-1-methylureido]-ldimethylaminomethylenelthiolcarbamatemethyl N[ l 3-phenyl- 1 -methylureido)- ldimethylaminomethylenel-thiolcarbamate methyl N- {l-[3-(3,4-dichlorophenyl) l methylureidoll -dimethylaminomethylene}thiolcarbamate methyl N- l {3-( 2,4,5-trichlorophenyl)- lmethylureido1- 1 -dimethylaminomethylene} thiolcarbamate methyl N-[ l-(3-norbomyl-l -methylureido)- l dimethylaminomethylenelthiolcarbamatemethyl N-[ l( 3-norbomenyl- 1 -methylureido l dimethylaminomethylene]thiolcarbam ate methyl N- i l 3-(cyclohexen-2-yl)- l -methylureido 1dimethylaminomethylenelthiolcarbamate ethyl N-[ l-( 3-cyclohexyll-methylureido) l dimethylaminomethylene ]thiolcarbamate isopropyl N-[l-( 3-cyclohexyll -methylureido) l 4dimethylaminomethylene]thiolcarbamate octyl N-ll-(3-cyclohexyl-l-methylureido)1- dimethylaminomethylenelthiolcarbamatemethyl N-[ l 1(3-cyclohexyl-l -methylureido)-l-(N-methyl-N-ethylaminomethylene ]carbamate methyl N[ l-( 3-cyclohexyllmethylureido)- l N- methyl -N-butylaminomethylene lcarbamate methyl N-[i-( 3-cyclohexyl- -methylureido)- l N- methyl-N-allylarninomethylene)Icarbamate methyl N-{ l-(3-cyclohexyl-l-methylureido) i (N-meIhyLN-propargylaminomethylene lcarbam ate methyl N- {l-[ 3-(p-methylthiophenyl)- l methylureido1- 1-dimethylaminomthylene}carbamatemethyl N-{l-[3-(p-methoxyphenyl)- l-methylureido1- l -dime thyiaminomethylene carbamate methyl N- ll 3-( 2,3,5,6-tetramethylcyclohexyl)- lmethylureidoll-dimethylaminomethylene}carba mate The compounds ofFormulas l and (2) can be used wherever general weed control is desired,for example, in industrial areas, railroad rightsof-way, and aroundhighway structures.

The precise amount of active material to be used in any given situationwill vary according to the plant species and soil involved, thefonnulation used, the mode of application, prevailing weatherconditions, foliage density, length of residual activity desired, andlike factors. it is, therefore, not possible to recommend a rate ofapplication suitable for all situations. Broadly speaking, the compoundsof the invention are used at levels of about 1 to about 25 kilograms perhectare.

The compounds of the present invention may be combined to any otherherbicide and are particularly useful in combination with3-sec-butyl-5-bromo-6- methyluracil (bromacil), 3-( 3,4-dichlorophenyl)-l ,1- dimethylurea (diuron), 1,1 '-dimethyl-4,4 bipyridinium salt(paraquat), 1,l -dimethyl-3-(3-N-tertbutylcarbamoyloxyphenyl)urea,4-amino-6-tert-butyl- 3-methylthio-as-triazin-S(4H )-one, ands'triazines such as 2-chloro-4-ethylamino-6-isopropylamino-s-triazine,for controlling a broad spectrum of weeds.

Many of the compounds of this invention possess unusually high watersolubility, up to several percent. This offers an advantage in, forinstance, control of brush and other deep-rooted, perennial weeds. Anexample of a highly water-soluble compound of this invention is methylN-( N-cyclohexylcarbamoyl-N ,N dimethylamidino)-N-methylcarbamate; thiscompound exhibits a solubility in water of about 22.7% at 25C.

The herbicidal activity of the compounds of this invention wasdiscovered in a greenhouse test. In this test seeds of crabgrass(Digitaria spp.), barnyardgrass (Echinochloa crusgalli), sorghum(Sorghum vulgare), wild oats (Avena falua), Cassia tora, morningglory(lpomoea spp.), radish (Raphanus spp.), marigold (Tagetes spp.), dock(Rumex crispus), and nutsedge (Cyperus rotundus) tubers were planted ina growth medium and treated preemergence at two rates l l and 2.2 kg.per hectare) with the chemical dissolved in a nonphytotoxic solvent.Johnsongrass (Sorghum halepense) having four leaves, crabgrass andbarnyardgrass with three leaves and nutsedge from tubers with two leaveswere treated postemergence at 11 kg per hectare, and bush beans with thethird trifoliate leaf ex panding and sorghum with four leaves weretreated postemergence at 2.2 kg per hectare. Treated plants and controlswere maintained in the greenhouse for 16 days, then all species werecompared to controls and visually rated for responses to treatment. Aquantitative rating was made on a scale of O to 10. A qualitative rating(type of injury) was also made.

The results obtained for methyl N-(N-cyclohexylcarbamoyl-N',N-dimethylamidino )-N- methylcarbamate (l) andmethyl N-[ l-( 3-cyclohexyll methylureido l -dimethylaminomethylene]carbamate (II) are shown in Table lll below, wherein 0 indicates noeffect and I0 means that all plants are affected, i.e.,

Handbook of Insecticide Dust Diluents and Carriers, 2nd. Edn., DorlandBooks, Caldwell, N.J., 1955. Less TABLE Ill Postemcrgencc PreemergenceCompound lOC lOC

lOC lOC lOC lOC

l 9C lOC lC lOC lOC lOC lOC lOC lOC lOC 10C 10C IOC lOC 10C Nutsedge.lohnsongrass Crabgrass Bamyardgrass Crabgrass Bamyardgrass Sorghum WildOats 5 Nutsedgc Casia Morningglory Mustard Radish Marigold Usefulformulations of the compounds of Formulas (l) and (2) can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wet-table powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew pints to several hundred gallons per acre. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 1% to 99% byweight of at least one compound of Formulas (l) and (2) and either about0.1% to l5% of a surfactant or about 1% to 99% of a solid or liquidcarrier or both. More specifically, the formulations will contain theseingredients in the following approximate proportions:

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable.

Typical solid carriers are described in Watkins, et al.,

5 and Emulsifiers Annual," Allured Pub]. C0rp., Ridgewood, N.J., as wellas Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Pbl.Co., lnc., New York, 1964, list surfactants and recommended uses. Allformulations can contain minor amounts of additives to reduce foam,caking, corrosion, microbiological growth, etc. Preferably, ingredientsshould be approved by the U.S. Environmental Protection Agency for theintended use.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques; see J. E. Browning, Agglomeration,ChemicalEngineering, Dec. 4, 1967, pp. l47ff. and Perrys Chemical EngineersHandbook," 4th. Edn., McGraw-Hill, N.Y., 1963, pp. 8-59ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361. R. W. Luckenbaugh, U.S. Pat. No.3,309,l92, H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855. G. C.Klingman, Weed Control as a Science," John Wiley and Sons, Inc., NewYork, 1961, pp. 81-96.

J. D. Fryer and S. A. Evans, Weed Control Handbook, 5th Edn. BlackwellScientific Publications, Oxford, 1968, pp. l0l-l03.

Typical formulations of compounds of the present invention are shownbelow:

A. Wettable Powder dimethylamidino)-Nmethylca.rbamate 40% Dioctyl sodiumsulfosuccinate l.5% Sodium ligninsulfonate 3% Low viscosity methylcellulose 1.5% Attapulgite 54% The ingredients are thoroughly blendedpassed through an air mill, to produce an average particle size under 15microns, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mmopening) before packaging.

B. Wettable Powder Methyl N-[ l-(3'cyclohexyl-l-methylureido)- 70% l-dimethylaminomethylene lcarbamate Sodium alkylnaphthalenesulfonate 2%Sodium N-methyl-N-oleoyltaurate 2% Diatomaceous earth 26% Theingredients are blended and ground in a hammer mill so that only a fewpercent of the active exceeds 250 microns (U.S.S. No. 60 sieve) in size.After milling, the powder is reblended and sifted through a U.S.S. No.50 sieve (0.3 mm opening) before packaging.

C. Water Soluble Powder Methyl N-(N-cyclohexylcarbamoyl-N',N'- 91.0%

dimethylamidino)-N-methylcarbamate Sodium alkylnaphthalenesulfonate 0.5%

Magnesium sulfate heptahydrate Synthetic fine silica D. Oil SuspensionMethyl N-lN-(3-methylphenylcarbamoyl)- 25% N ,N '-dimethylamidino]-N-methylcarbamate Polyoxyethylene sorbitol hexaoleate 7%;

Highly aliphatic hydrocarbon oil The ingredients are ground together ina sand mill until the solid particles have been reduced to under aboutmicrons. The resulting thick suspension may be applied directly, butpreferably after being extended with oils or emulsified in water.

The ingredients are blended, hammer milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be 5 crushed to pass aU.S.S. No. sieve (0.84 mm openings). The granules held on a U.S.S. No.40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

In the following composition claims, the expression consistingessentially of means that, in addition to the components recited inthose claims, other components also may be present, provided they do notadversely affect the operability of the compositions for their intendeduse.

I claim:

1. A compound having the following formula wherein R is selected from aC -C cycloalkyl substituted with 0-1 C -C alkyl, 0-2 methyl groups, O2chlorine or bromine atoms, or O-l methoxy or ethoxy group; a C -Ccycloalkenyl; a C -C cycloalkylmethyl or cycloalkenylmethyl; a C -Cbicycloalkyl or bicycloalkenyl; a Cg-Cu bicycloalkylmethyl 0rbicycloalkenylmethyl; trimethylcyclohexyl; tetramethylcyclohexyl;

R2 is a C4-C3 R is hydrogen, methyl, or ethyl;

R is a C C alkyl, a C -C alkenyl, a C -C alkenyl;

R is OR wherein R is a C -C alkyl substituted with 0-3 chlorine atoms orO-l methoxyl; and

X is oxygen.

2. A compound of claim 1 wherein R is a C -C cycloalkyl, or a C -Ccycloalkyl substituted with one methyl group; each of R R and R ismethyl; and R, is OR,,.

3. A compound of claim 2 wherein R, is cyclopentyl, methylcyclopentyl,cyclohexyl, or methylcyclohexyl; X is oxygen; and R, is methoxyl.

4. Methyl N-[ 1-( S-cyclohexyll -methylureido)- ldimethylaminomethylenelcarbamate, a compound of claim 3, wherein R iscyclohexyl.

l I i l l

1. A COMPOUND HAVING THE FOLLOWING FORMULA
 2. A compound of claim 1wherein R1 is a C5-C8 cycloalkyl, or a C5-C8 cycloalkyl substituted withone methyl group; each of R2, R3, and R4 is methyl; and R5 is -OR6.
 3. Acompound of claim 2 wherein R1 is cyclopentyl, methylcyclopentyl,cyclohexyl, or methylcyclohexyl; X is oxygen; and R5 is methoxyl. 4.MethylN-(1-(3-cyclohexyl-1-methylureido)-1-dimethylaminomethylene)carbamate, acompound of claim 3, wherein R1 is cyclohexyl.